EP0139788B1 - A method for a controlled change of the pore size in solids - Google Patents
A method for a controlled change of the pore size in solids Download PDFInfo
- Publication number
- EP0139788B1 EP0139788B1 EP83201516A EP83201516A EP0139788B1 EP 0139788 B1 EP0139788 B1 EP 0139788B1 EP 83201516 A EP83201516 A EP 83201516A EP 83201516 A EP83201516 A EP 83201516A EP 0139788 B1 EP0139788 B1 EP 0139788B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pore size
- process according
- deposit
- gas
- zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011148 porous material Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 17
- 239000007787 solid Substances 0.000 title claims description 7
- 239000010457 zeolite Substances 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003039 volatile agent Substances 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005549 size reduction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical class [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
- B01J2229/126—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to reduce the pore-mouth size
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S95/00—Gas separation: processes
- Y10S95/90—Solid sorbent
- Y10S95/902—Molecular sieve
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
Definitions
- This invention relates to a method for pore size modification in such a way that specific molecular sieving effects can be obtained by controlled pore size reduction and that encapsulation of compounds elements or ions can be performed by pore closure.
- porous materials such as zeolites
- ion exchange ion exchange
- a purely physical sorption or ion exchange however is an equilibrium process, depending on concentration, pressure temperature etc. It is therefore essentially reversible and not suitable for immobilising ions or molecules in a stable manner in a solid matrix.
- the European patent 80103117.0 (Penzhorn) describes a similar method for encapsulating gas molecules under high pressures and high temperature in zeolites.
- the encapsulation is based on a thermal vitrification of the zeolite in the presence of a pressurised gas. Under this pressure, and at higher temperature, the zeolite transforms into amorphous stable material, containing the enclosed gas molecules.
- the European patent 81201137.7 describes the possibility to encapsulate gas molecules and other molecules by closing or narrowing the zeolite pores after sorption under normal conditions of temperature and pressure.
- the pore size reduction is obtained by a structural modification process, based on chemisorption of a modifier such as SiH 4 , B 2 H 6 , etc. on structural hydroxyl groups, followed by further reaction with 0 2 , H 2 0, CH 3 0H, etc.
- Process for changing the pore size of a porous solid in which a degassed solid is treated in two stages with two chemisorbable materials in order to form a deposit in at least the entrance of the pores, one of these materials being diborane (B Z H 6 ), and if desired these stages are repeated until the desired pore size is obtained, characterized in that the other material consists of a volatile compound of nitrogen or phosphorus, which can react with diborane to form a deposit.
- a mordenite sample was degassed (dehydrated) in a vacuum at 450°C and 1.95 meq NH 4 '/g dry material was then adsorbed. Following treatments were applied: boranation at 20°C, heating at 150°C, boranation at 150°C, heating at 400°C, oxidation with H 2 0 and dehydration at 400°C. After each step sorption capacities were measured. The results, tabulated below, indicate that a small boranation results in a dramatic exclusion of N 2 at -196°C. At 150°C boranation reactions proceed intensively, and a further strong pore size reduction is observed. After oxidation, adsorption appears to be limited to the external surface and the zeolite pores are closed completely. An argument for NH 3 to be really involved in the reactions is the fact that deammoniation did not occur when the zeolite was heated at 400°C after boranation.
- a mordenite sample was prepared in its H-form, dehydrated in a vacuum at 400°C and reacted with 1,60 mmol B 2 H 6 per g mordenite at 150°C. Then the boranated sample was reacted with NH 3 at room temperature. During this reaction H 2 was evolved, indicating a real reaction between the NH 3 and the BH n groups in the zeolite. When heated at 400°C, again H 2 was evolved and only a small amount of NH 3 was liberated by the zeolite. Deammoniation did not occur and therefore formation of stable B-N bonds in the zeolite is concluded. When treated with water, again a small amount of H 2 was evolved. The sorption properties are measured after each step, and tabulated below.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
- This invention relates to a method for pore size modification in such a way that specific molecular sieving effects can be obtained by controlled pore size reduction and that encapsulation of compounds elements or ions can be performed by pore closure. It is known that porous materials, such as zeolites, can adsorb gases and other materials and that they can take in ions by ion exchange, provided that the pores of the substrate are large enough. A purely physical sorption or ion exchange however is an equilibrium process, depending on concentration, pressure temperature etc. It is therefore essentially reversible and not suitable for immobilising ions or molecules in a stable manner in a solid matrix.
- In US patent 3,316,691, it is proposed to encapsulate gases or fluids in a suitable zeolite, whose pores are not large enough to take in the molecules concerned. In that process the molecules are forced into the structure at high temperatures (250-350°C) and high pressures (2000 bar). After cooling to room temperature, the pressure is released, and the molecules remain trapped in the zeolite.
- The European patent 80103117.0 (Penzhorn) describes a similar method for encapsulating gas molecules under high pressures and high temperature in zeolites. The encapsulation, however, is based on a thermal vitrification of the zeolite in the presence of a pressurised gas. Under this pressure, and at higher temperature, the zeolite transforms into amorphous stable material, containing the enclosed gas molecules.
- The European patent 81201137.7 describes the possibility to encapsulate gas molecules and other molecules by closing or narrowing the zeolite pores after sorption under normal conditions of temperature and pressure. The pore size reduction is obtained by a structural modification process, based on chemisorption of a modifier such as SiH4, B2H6, etc. on structural hydroxyl groups, followed by further reaction with 02, H20, CH30H, etc.
- Process for changing the pore size of a porous solid, in which a degassed solid is treated in two stages with two chemisorbable materials in order to form a deposit in at least the entrance of the pores, one of these materials being diborane (BZH6), and if desired these stages are repeated until the desired pore size is obtained, characterized in that the other material consists of a volatile compound of nitrogen or phosphorus, which can react with diborane to form a deposit.
- In the present application we claim very stable effective pore size reductions by using reactions of nitrogen (or phosphorous) compounds such as NH3, NH4 or their alkyl derivatives or compounds such as pyridine etc. with diborane in aluminosilicates or zeolites (hereafter called the "material"). A possible example is given below:
- Similar reactions can occur when these compounds react with each other in any zeolite or clay mineral, whatever its structure, chemical composition or ionic form is. However, analogous reactions take place if one of the reaction components is previously chemisorbed on the substrate. If BZH6 is previously chemisorbed in a H zeolite, the reaction of NH3 or other N or P compounds with the boranated samples is carried out, and a further pore size reduction is obtained. Another type of procedure consists in reaction of diborane in zeolites, which have been subject to chemisorption of NH3 or other N or P compounds. In addition, successive alternating treatments with NH3 and with B2H6 are possible. Boron-nitrogen compounds, connected to the structural framework of the substrate, are formed, yielding stable obstructions with a strong pore size reducing effect. Of course, these reactions can always be combined in many ways with hydrolysis reactions such as reactions with structural OH groups and/or hydration water.
- A mordenite sample was degassed (dehydrated) in a vacuum at 450°C and 1.95 meq NH4'/g dry material was then adsorbed. Following treatments were applied: boranation at 20°C, heating at 150°C, boranation at 150°C, heating at 400°C, oxidation with H20 and dehydration at 400°C. After each step sorption capacities were measured. The results, tabulated below, indicate that a small boranation results in a dramatic exclusion of N2 at -196°C. At 150°C boranation reactions proceed intensively, and a further strong pore size reduction is observed. After oxidation, adsorption appears to be limited to the external surface and the zeolite pores are closed completely. An argument for NH3 to be really involved in the reactions is the fact that deammoniation did not occur when the zeolite was heated at 400°C after boranation.
- A CH3NH3 +-mordenite was reacted with B2H6 and the exclusion for Kr and N2 was followed:
- A mordenite sample was prepared in its H-form, dehydrated in a vacuum at 400°C and reacted with 1,60 mmol B2H6 per g mordenite at 150°C. Then the boranated sample was reacted with NH3 at room temperature. During this reaction H2 was evolved, indicating a real reaction between the NH3 and the BHn groups in the zeolite. When heated at 400°C, again H2 was evolved and only a small amount of NH3 was liberated by the zeolite. Deammoniation did not occur and therefore formation of stable B-N bonds in the zeolite is concluded. When treated with water, again a small amount of H2 was evolved. The sorption properties are measured after each step, and tabulated below.
Claims (9)
1. Process for changing the pore size of a porous solid, in which a degassed solid is treated in two stages with two chemisorbable materials in order to form a deposit in at least the entrance of the pores, one of these materials being diborane (B,H,), and if desired these stages are repeated until the desired pore size is obtained, characterized in that the other material consists of a volatile compound of nitrogen or phosphorus, which can react with diborane to form a deposit.
2. Process according to claim 1, characterized in that the porous solid is an aluminosilicate.
3. Process according to claim 2, characterized in that the aluminosilicate is a zeolite.
4. A process according to claim 3, characterized in that the zeolite is mordenite.
5. Process according to claims 1-4, characterized in that the compound of nitrogen is ammonia, an alkyl amine, or pyridine.
6. Process according to claims 1-5, characterized in that the deposit is formed at a temperature between room temperature and 200°C.
7. Process according to claims 1-6, characterized in that the pore size can be increased again by heating the material to a temperature above that at which the deposit was formed.
8. Process for fixing an adsorbable gas in which the gas is adsorbed in a porous material, characterized in that the material is one which has been prepared according to claims 1-7, such that its pore size makes it selective for the gas to be adsorbed or results in encapsulation of the adsorbed gas.
9. Process according to claim 8, characterized in that after the adsorption of the gas any remaining diborane is inactivated by oxidation with water or steam in order to swell the deposit and to further close the pores.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE8383201516T DE3366121D1 (en) | 1983-10-21 | 1983-10-21 | A method for a controlled change of the pore size in solids |
| EP83201516A EP0139788B1 (en) | 1983-10-21 | 1983-10-21 | A method for a controlled change of the pore size in solids |
| US06/662,223 US4620857A (en) | 1983-10-21 | 1984-10-18 | Method for a controlled change of the pore size in solids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP83201516A EP0139788B1 (en) | 1983-10-21 | 1983-10-21 | A method for a controlled change of the pore size in solids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0139788A1 EP0139788A1 (en) | 1985-05-08 |
| EP0139788B1 true EP0139788B1 (en) | 1986-09-10 |
Family
ID=8191004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83201516A Expired EP0139788B1 (en) | 1983-10-21 | 1983-10-21 | A method for a controlled change of the pore size in solids |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4620857A (en) |
| EP (1) | EP0139788B1 (en) |
| DE (1) | DE3366121D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199854B1 (en) * | 1985-05-01 | 1990-01-31 | European Atomic Energy Community (Euratom) | Process for ultra-drying of a gas |
| DE3880819T2 (en) * | 1988-02-11 | 1993-08-19 | Air Liquide | GAS SEPARATION. |
| NL8901240A (en) * | 1989-05-18 | 1990-12-17 | Pelt & Hooykaas | PROCESS FOR IMMOBILIZING ENVIRONMENTALLY HARMFUL METALS AND ORGANIC SUBSTANCES. |
| AU2002258956A1 (en) * | 2001-04-20 | 2002-11-05 | University Of Southern California | Ship-in-a-bottle catalysts |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3305656A (en) * | 1963-12-26 | 1967-02-21 | Gen Electric | Electrical insulation containing a molecular sieve having adsorbed perhalogenated fluid |
| US3442819A (en) * | 1965-03-26 | 1969-05-06 | Mount Sinai Hospital Research | Molecular sieve coated particulate adsorbent and processes using same |
| BE690862A (en) * | 1965-12-13 | 1967-06-08 | ||
| US3316691A (en) * | 1966-05-31 | 1967-05-02 | Union Carbide Corp | Fluid encapsulation product |
| US3536521A (en) * | 1967-12-01 | 1970-10-27 | Grace W R & Co | Coating of molecular sieves |
| US3658696A (en) * | 1969-06-17 | 1972-04-25 | Texaco Inc | Selected adsorption with a silanized crystalline alumino-silicate |
| US3698157A (en) * | 1971-06-01 | 1972-10-17 | Mobil Oil Corp | Separation of mixtures with modified zeolites |
| US3724170A (en) * | 1971-09-13 | 1973-04-03 | Mobil Oil Corp | Staged separations of aromatic mixtures with zeolites |
| DE2305435C3 (en) * | 1973-02-03 | 1979-08-09 | Bergwerksverband Gmbh, 4300 Essen | Carbonaceous molecular sieves |
| US4090981A (en) * | 1976-09-23 | 1978-05-23 | Mobile Oil Corporation | Catalyst for selective production of para dialkyl substituted benzenes |
| DE2948515C2 (en) * | 1979-12-01 | 1983-12-22 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | Method for the fixation of radioactive noble gases |
| NL8005645A (en) * | 1980-10-13 | 1982-05-03 | Euratom | METHOD FOR REVERSIBLE STORAGE OF GASES OR VAPORS IN A NATURAL OR SYNTHETIC ZEOLITE |
| EP0049936B1 (en) * | 1980-10-13 | 1985-04-03 | European Atomic Energy Community (Euratom) | A method of encapsulating materials in a zeolite in a stable manner |
-
1983
- 1983-10-21 DE DE8383201516T patent/DE3366121D1/en not_active Expired
- 1983-10-21 EP EP83201516A patent/EP0139788B1/en not_active Expired
-
1984
- 1984-10-18 US US06/662,223 patent/US4620857A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0139788A1 (en) | 1985-05-08 |
| DE3366121D1 (en) | 1986-10-16 |
| US4620857A (en) | 1986-11-04 |
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